• Bulletin of the Korean Chemical Society
• /
• 제12권2호
• /
• pp.182-188
• /
• 1991

The reactions of aniline with benzyl and phenacyl compounds are studied by the AM1 method. Two types of modeling were adopted: Cation-neutral, in which a proton is attached to the leaving group F and anion-neutral model, in which aniline was replaced by phenoxide with Cl as the leaving group. The cation-neutral model represented the reactvery well, reproducing the various solution-phase experimental results. In the benzyl system, the ${\pi}$-electrons of the two rings (X-ring in the nucleophile and Y-ring in the substrate) interact conjugatively in the transition state (TS) resulting in a bond contraction of the $C_{\alpha}-C_{Y1}$ bond (benzylic effect), whereas in the phenacyl system the ${\pi}$ electrons of the X-ring delocalizes more efficiently into the carbonyl group than into the Y-ring (resonance shunt effect) with a bond contraction of the $C_{\alpha}-C_{\beta}$ bond. The bond contraction in the benzylic effect was substantially greater than that in the resonance shunt effect. The TS was rather loose for benzyl while it was tighter for phenacyl system. Various bond length changes with substituents in the TS were, however, found to be irregular.

• 한국미생물·생명공학회지
• /
• 제40권2호
• /
• pp.163-167
• /
• 2012

D-Xylose는 Saccharomyces cerevisiae에서 기질로 이용될 수 없어 S. cerevisiae가 이용 가능한 D-xylulose로의 전환이 요구된다. 효소고정화 시스템을 통한 D-xylose로부터 D-xylulose로의 전환을 위해 대장균의 D-xylose 이성화효소(XI)의 카르복시 말단에 양이온 교환수지를 이용한 단순 정제 및 고정화가 가능하도록 10-arginine tag(R10)을 융합하였다. 융합단백질인 XIR10은 재조합 대장균에서 과잉발현되었고 단일 단계의 양이온 교환 크로마토그라피를 통하여 고순도로 정제되었다. 정제된 XIR10은 카르복시 말단의 10-arginine tag과의 정전기적 상호작용을 통하여 양이온 교환수지에 고정화되었다. 고정화 및 비고정화된 XIR10은 넓은 범위의 pH 및 온도에서 비슷한 D-xylose 이성화효소 활성을 보였다. 이 결과는 양이온 교환수지로의 고정화는 XIR10의 효소적 기능에 영향을 주지 않는다는 것을 나타낸다. 고정화된 XIR10의 최적화된 조건에서 D-xylose의 25%는 D-xylulose로 이성화되었다. 본 연구의 결과들은 10-arginine tag과 양이온 교환수지간의 상호작용을 통해 정전기적 고정화된 XIR10이 D-xylose로부터 D-xylulose로의 전환에 응용 가능하다는 것을 명확하게 보여주었다.

• Applied Biological Chemistry
• /
• 제2권
• /
• pp.45-52
• /
• 1961

The decomposition of malathion in dust for mulations prepared from four Korean tales as carriers during storage period has been studied. Amberlite CG-120, a cation exchange resin . which has higher cation exchange capacity than tales, was also used as a carrier in hope of finding out the effect of nagative charge upon the decomposition of malathion. Besides the original talc powders obtained directly from the mines, the hydrogen ion saturated forms were also used as carriers for comparisonal study. The saturated ions for the resin were hydrogen, sodium and magnesium. As the physical properties of the tales, colloid content, water adsorption capacity, PH, specific surface, phosphate fixing capacity and exchangeable canons were determined, and these properties were correlated with the amount of the decomposition. Following results were obtained from the experiment. 1. The malathion in the talc in dust was found to decompose around 10-15% ofthe total withina month. About 50% of the decom position that took place after a month was found to occur within a week. 2. The resin which has higher cation exchange capacity than the tales was highly effective in the decomposition of malathion compared with the tales. 3. In every case the saturation of the exchange complexes with hydrogen ion greatly accelerated the decomposition of malathion. 4. The most highly correlated physical properties with the decomposition were colloid content and specific surface of the tales. 5. The water adsorption and phosphate fixing capacities of the tales were found not to correlate with the amount of malathion decomposed. From the experimental results it was concluded that the active negative spots on the colloidal tales or the resin attract the electropositive phosphorus atom in a malathion molecule thereby inducing the decomposition easier. The presence of hydrogen ion nearby might cause a catalytic effect in the decomposition of malathion.

• Corrosion Science and Technology
• /
• 제9권1호
• /
• pp.20-28
• /
• 2010

According to the bipolar model, ion selectivity of some species in the passive film is important factor to control the passivation. An increase of cation selectivity of outer layer of the passive film can stabilize the film and improves the corrosion resistance. Therefore, the formation and roles of ionic species in the passive film should be elucidated. In this work, two types of solution (hydrochloric or sulfuric acid) were used to test high N and Mo-bearing stainless steels. The objective of this work was to investigate the formation of oxyanions in the passive film and the roles of oxyanions in passivation of stainless steel. Nitrogen exists as atomic nitrogen, nitric oxide, nitro-oxyanions (${NO_x}^-$), and N-H species, not nitride in the passive film. Because of its high mobility, the enriched atomic nitrogen can act as a reservoir. The formation of N-H species buffers the film pH and facilitates the formation of oxyanions in the film. ${NO_x}^-$ species improve the cation selectivity of the film, increasing the oxide content and film density. ${NO_x}^-$ acts similar to a strong inhibitor both in the passive film and at active sites. This facilitates the formation of chromium oxide. Also, ${NO_x}^-$ can make more molybdate and nitric oxide by reacting with Mo. The role of Mo addition on the passivation characteristics of stainless steel may differ with the test environment. Mo exists as metallic molybdenum, molybdenum oxide, and molybdate and the latter facilitates the oxide formation. When nitrogen and molybdenum coexist in stainless steel, corrosion resistance in chloride solutions is drastically increased. This synergistic effect of N and Mo in a chloride solution is mainly due to the formation of nitro-oxyanions and molybdate ion. Oxyanions can be formed by a 'solid state reaction' in the passive film, resulting in the formation of more molybdate and nitric oxide. These oxyanions improve the cation selectivity of the outer layer and form more oxide and increase the amount of chromium oxide and the ratio of $Cr_2O_3/Cr(OH)_3$ and make the film stable and dense.

• 한국의학물리학회지:의학물리
• /
• 제17권2호
• /
• pp.96-104
• /
• 2006

본 연구자를 위시한 많은 연구자에 의해 칼슘이 N형 칼슘통로의 비활성화를 촉진시킨다는 것이 보고되었다. 그러나 칼슘에 의한 비활성화 촉진 효과가 고전적인 칼슘의존성 기전에 의해 기인하는지는 아직 확실하지 않다. L형 칼슘통로의 칼슘의존성 비활성화기전을 밝히기 위하여 지금까지 사용해온 방법의 하나는 세포내, 외의 칼슘농도를 변화시켜보는 것이다. 그러므로 본 연구에서는 칼슘의존성 비활성화기전의 존재 여부를 알아보기 위하여 2가 양이온을 1가 양이온인 메틸아민($MA^+$)으로 치환하였다. 선행 연구를 통해 우리는 5초 동안의 긴 저분극 자극 시 바륨과 칼슘을 사용하여 얻은 전류에서 모두 빠른 성분(${\tau}{\sim}150ms$)과 느린 성분(${\tau}{\sim}2,500ms$)의 비활성화가 있음을 알 수 있었다. 본 연구에서 세포외 2가 양이온의 농도가 0이 되도록 하였을 때 빠른 비활성화가 소실된 반면 느린 비활성화에는 영향이 거의 없었다. 또한 바륨를 사용하였을 때보다 10 mV씩 과분극시킨 전압에서의 메틸암모늄 전류 데이터를 비교하여 보았을 때 느린 비활성화의 시정수가 서로 잘 일치하였으며 이 시정수는 막전압이 저분극될수록 감소하는 막전압의존성 비활성화의 특성을 보였다. 본 연구결과와 선행연구의 결과를 종합하여 볼 때 세포외 2가 양이온의 존재는 N형 칼슘통로의 빠른 비활성화가 일어나기 위하여 필수적인 조건이며 이러한 2가 양이온의존성 비활성화기전은 기존의 칼슘의존성 또는 막전압의존성 기전과 다르다는 가설을 제안한다.

• The Korean Journal of Physiology and Pharmacology
• /
• 제5권5호
• /
• pp.373-380
• /
• 2001

The action of opioid on the hyperpolarization-activated cation current $(I_h)$ in substantia gelatinosa neurons were investigated by using whole-cell voltage-clamp recording in rat spinal brain slices. Hyperpolarizing voltage steps revealed slowly activating currents in a subgroup of neurons. The half-maximal activation and the reversal potential of the current were compatible to neuronal $I_h.$ DAMGO $(1\;{\mu}M),$ a selective- opioid agonist, reduced the amplitude of $I_h$ reversibly. This reduction was dose-dependent and was blocked by CTOP $(2\;{\mu}M),$ a selective ${\mu}-opioid$ antagonist. DAMGO shifted the voltage dependence of activation to more hyperpolarized potential. Cesium (1 mM) or ZD 7288 $(100\;{\mu}M)$ blocked $I_h$ and the currents inhibited by cesium, ZD 7288 and DAMGO shared a similar time and voltage dependence. These results suggest that activation of ${\mu}-opioid$ receptor by DAMGO can inhibit $I_h$ in a subgroup of rat substantia gelatinosa neurons.

• 산업기술연구
• /
• 제39권1호
• /
• pp.41-45
• /
• 2019

Hydrogen sulfide ($H_2S$) is mainly produced along with methane and hydrocarbons in many gas fields as well as hydrodesulfurization processes of crude oils containing sulfur compounds and the emission of $H_2S$ has a considerable effect on both environmental problem and human health aspects due to formation of, e.g. acid rain and smog. In recent years, ionic liquids (ILs) have been proposed as the most promising solvents for $CO_2$ and hazardous pollutants capture, such as $H_2S$ and sulfur dioxide ($SO_2$). In this work, we demonstrate the use of the predictive COSMO-SAC model for the prediction of Henry's law constant of $H_2S$ in ILs. Furthermore, the method is used to screen for potential IL candidates for $H_2S$ capture from a set of 2,624 ILs formed from 82 cations and 32 anions. The effects of cation on the Henry's law constant of $H_2S$ such as (i) the variation of the alkyl chain length on cation, (ii) the substituent of methyl group ($-CH_3$) for H in C(2) position and (iii) the change of ring structure for cation family are clearly predicted by COSMO-SAC model.

• 한국세라믹학회지
• /
• 제36권1호
• /
• pp.50-54
• /
• 1999

양이온 결손 La0.970Mn0.970O3의 x-ray photoemission spectroscopy를 온도를 함수로 측정하였다. 온도의 변화에 따라서 Mn 2p와 3d core level의 화학적 변동 및 이동이 관측되었다. 즉 Mn 2p 3/2와 1/2 및 La 3d core 스펙트럼은 온도의 증가와 함께 저 결합 에너지 측으로 이동이 관측되었다. 이러한 XPS 관측 결과는 Mn3+의 localization의 강도 변화에 의한 것으로 사료되며, Mn3+에 의한 Jahn-Teller효과 이외에도 conventional random potential 효과 역시 La0.790Mn0.970O3의 전도 carrier의 localization에 기여하는 것으로 사료된다.

• Bulletin of the Korean Chemical Society
• /
• 제35권4호
• /
• pp.1117-1120
• /
• 2014

Ru/C-catalyzed hydrogenation of m-xylylene diamine into 1,3-cyclohexanebis(methylamine) was greatly accelerated by the presence of $LiNO_3$, $NaNO_2$, or $NaNO_3$. It was found that the effect of the nitrate salt was significantly affected by the size of cation. The promoting effect of the nitrate salt increased with the decrease of the cation size: $LiNO_3$ ~ $NaNO_2$ > $KNO_3$ > $CsNO_3$ >> [1-butyl-3-methylimidazolium]$NO_3$. XRD analysis of the recovered catalysts after the hydrogenation reactions showed that $LiNO_3$ and $NaNO_2$ were completely transformed into LiOH and NaOH, respectively, along with the evolution of $NH_3$, while $KNO_3$ and $CsNO_3$ remained unchanged.

• 대한화학회지
• /
• 제27권1호
• /
• pp.18-23
• /
• 1983

희토류 양이온이 4M 이상의 염산과 과염소산 용액에서 양이온 교환지수에 예상보다도 큰 흡수를 나타내는 현상을 알아보기 위하여, $1{\sim}12M 염산 또는 염산-과염소산 혼합용액에서 Dowex 50W-X2 양이온 교환지수에 흡수되는 Ce(III), Tb(III) 및 $Cl^-$이온의 양을 흡광분광법으로 측정하였다. 염산-과염소산 혼합용액에서 Ce(III)와 Tb(III)의 %S(흡수백분율) 값은 염산용액의 값에 비하여 모든 산농도에서 증가하였으며, 혼산중 과염소산의 분율이 증가함에 따라 과염소산만의 %S에 접근하는 것을 관찰하였다. 또 $Cl^-$ 이온의 흡수를 염산의 농도에 따라 측정해 봄으로써 수지내에서는 희토류 양이온과 $Cl^-$이온간의 착물로 존재하는 양은 많아야 흡수된 전체 희토류 이온의 10%에 불과해서 수지내에서의 이러한 착물형성이 중요하지 않은 것을 알았다. 혼산중의 과염소산 분율이 증가함에 따라 수지내 착물형성의 경향이 더욱 감소하였으므로 %S의 증가현상은 Cl-이온보다는 $ClO_4^-$이온의 영향이 더 클 것으로 예상된다.